Pyrazolyl-triazolyl coumarins

ABSTRACT

7 - (PYRAZOLYL - (1))-3-(1,2,4-TRIAZOLYL-(1)-)COUMARINS AND THEIR QUATERNIZATION PRODUCTS, ADAPTED FOR USE AS BRIGHTENING AGENTS, ARE PREPARED BY CONDENSING (-HYDRAZINO-3-(1,2,4-TRIAZOLYL(1))-COUMARINS WITH 1,3 - DICARBONYL COMPOUNDS AND OPTIONALLY QUATERNIZING THAT PRODUCT.

Un t d S s Pat 3,663,560 I v PYRAZOLYL-TRIAZOLYL COUMARINS Carl-Wolfgang Schellhammer, Opladen, Alfons Dorlars,

Leverlmsen, and, Wolf-Dieter Wirth, Cologne-Stammheim, Germany, assiguors to Farbenfabriken Bayer gesl schattfLexerk lse ,.Getmau g; No Drawing. Filed May 13, 1968, Ser. No. 728,800 Claims priority, applicatitsnzl fgrmany, May 22, 1967,

ABSTRACT on THE DISCLOSURE 7 [pyrazolyl (l)]-3-[1,2,4-triaZolyl (l)-]-coumarins and their quaterniz'ation products, adapted for use as brightening agents, are prepared by condensing 7-hydrazino-3-[l,2,4-triazolyl(l)]-coumarins with 1,3 dicarbonyl compounds and optionally quaternizing that product;

The object of the present invention comprises new, fluorescent, practically colourless 7 [pyrazolyl (l )]-3- [1,2,4-triazolyl-(1)]-coumarin derivatives of the general 1) e I aralkyl in which R -R have the same meaning as above,

stands for an optionally substituted alkyl or radical, and X(-) represents an anion..

' Examples of optionally substituted alkyl radicals in clude the following: CH C H C H C4H CHgCl, CH2OCH3. I i

Optionally substituted aralkyl radicals include, for example, radicals such as in which R; and R stand for a lower alkyl group, and the aromatic nucleus 3,6635% Patented May 16, 1972 ents, such as halogen, particularly chlorine and bromine, cyano, alkyl, alkoxy, canboxyl, acylamino, sulphonic acid, sulphonamide,:carbonamide or alkyl-sulphone groups.

Suitable radicals of this type are, for example, chlorophenyl, dichlorophenyl, .methoxyphenyl, ethoxyphenyl,

carbonmethoxyphenyl, 'carboethoxyphenyl, carbonamidophenyl and. carboxyphenyl.

Halogen atoms are, in particular, chlorine and V bromine. 10 2 Claims Y -fThe-anionaX. ispreferably a colourless anion which is either derived from the quaternising agent used, or has been introduced by subsequent exchange of the anion J: present from the production for any other anion, preferably a colourless anion.

As:,anions there may be used, for example CK Br sulphonate groups, such as OSO CH paratoluene-sulphonate, benzene sulphonate, phosphate, acetate, chlorozincate, perchlorate, nitrate, sulphate and oxalate radicals.

The compounds of the Formula I can be prepared in f the following manner: 1,2,4-triazolyl-(1)-acetic acids of may contain further substituents' v 1.. Suitable aralkyl radicals are the following, for example: t

The term optionally substituted aryl radicals preferably comprises phenyl radicals which may contain substituthe general formula N-CHz-C 0 OH R, (III) in which R, and R have the same meaning as above, are reacted with 4-acetylamin0-salicyliden-aniline in the presence 'of sodium acetate an dacetic anhydride at C. to give 7-acetylamino-3-[1,2,4-triazolyl-(1)]- coumarins of the general formula in which R and R have the same meaning as above. The acyl radical was split off by a dilute mineral acid, such as hydrochloric acid, or by dilute sulphuric acid, the resultant 7-amino-3 1,2,4-triazolyl-(1) ]-courarin of the general formula in which R, and R have the same meaning as above, is diazotised in a mineralacid solution, the diazonium salt reduced, e.gl with tin(II)-chloride in a hydrochloric acid solution, to give the 7 hydrazino compound of the general formula HzH-NH- 0 --O R4 .in which R and R have the same meaning as above. These hydrazines yield 7-[pyrazolyl-'(l)]-3-[1,2,4-tri- 'azolyl- (1)]-coumarins of the general Formula I in the reaction with 1,3-dicarbonyl compounds of the general formula 4 in which R, to R have the same meaning as above, or with functional derivatives of the 1,3-dicarbonyl com- TABLE A. COMPOUNDS OF THE FORMULA (1) pounds, such as, for example, acetals or ketals of these compounds, in an organic, aqueous organic or in a min- H H H' H H eral acidic aqueous solution at temperatures of about 5 E g 80-130 C., and, if acetals or ketals are used, it is nec- CH3 H CH3 H H essary to acidity the medium with a mineral acid in org g der to split off the protective group. H H CuHs H H The compounds of the general Formula II are obtained 8%? g by the reaction of compounds of the Formula I with OH: H CH3 CH1 CH; quaternising agents in known manner,-for example in an TABLE B.COMPOUNDS OF THE FORMULA (II) R1 R2 R3 R4 R5 I Rs X- H H H H H CH CH3SO49 CH, H H H H CH3 CHBSOAG CH3 H H H H CZHIS CzH SO4 H H H H H C2H5 02115804 H Cl H H H CH; CH3SO46 H C1 H H H C2H5 CH3SO49 CH3 H OH; H H CH3 CH3SO46 OH; H H H H CH3 CH3 H CH CH CH3 CH3 CHFQSMG H H OH; H H CH; cfizsol OH; H H H H (n)CrHu m OH; H H H H C1 inert organic solution. Suitable alkylating agents are, for Those compounds of the Formula I or II are preferred example, the esters of strong mineral acids and organic in which R stands for hydrogen, CH and phenyl, R -R sulphonic acids with, preferably, low molecular weight stand for hydrogen, and R stands for CH and X- is alcohols, such as alkyl chlorides, alkyl bromides, aralkyl an anion. halides, dialkyl sulphates and esters of sulphonic acids The brightening agents according to the present invenof the benzene series, such as methyl, ethyl, propyl ntion can be used in conventional manner, for example, butyl esters of benzene sulphonic acid, of the p-methylin the form of solutions in water or in organic solvents, benzene sulphonic acid, p-chlorobenzene sulphonic acid or in the form of aqueous dispersions. Polyester mateand p-nitrobenzene sulphonic acid. rials can be treated with the brightening agents in such As inert organic solvents there may be used, for exa way that they are impregnated with solutions or disample, higher boiling aliphatic, cycloaliphatic or oramotic persions of the brightening agents, then squeezed, dried hydrocarbons, furthermore stable aliphatic or cyclic haloand heated for a short period of time at temperatures gen compounds, such as carbon tetrachloride, tetrachloabove 150 C. The brightening agents can also be added roethylene, monoor dichlorobenzene, and nitrobenzene. to casting and spinning solutions which serve for the When avoiding too violent reaction conditions, it is also production of synthetic fibres, filaments, foils and other possible to operate in an excess of liquid quaternising articles. The necessary quantities can readily be deteragent. mined in each case; in general, amounts of 0.1% to 0.5%, l,2,4-triazolyl-(1)-acetic acid is known. Triazolyl-(l)- referredto the material to be brightened, have proved to acetic acids with substituents R and R can be obtained be sufficient. by reacting correspondingly substituted 1,2,4triazoles The brightening agents according to the invention have with halo-ethyl acetates, e.g. bromo-ethyl acetate or chloan extraordinary high yield. They are stable towards ro-ethyl acetate, and subsequent hydrolysis of the 3,5- chlorite-containing bleaching baths and the brightening disubstittued 1,2,4-triazolyl-(1)-ethyl acetate. efiects attained are very fast to light.

i1,3-dicarbonyl compounds which are suitable for the reaction with 7-hydrazino-3-[1,2,4-triazolyl-(l)]-couma- "EXAMPLE 1 rins r f p m n-(dD I hY 0r m l n-( Polyacrylonitrile fibres are introduced, in a goods-toaldehydetetl'aalkyl acetal, y yd 0 3* liquor ratio 1:40, into an aqueous bath containing, per butyraldehydedimethylacetal, benzoylacetaldehyde or litre, .1 g. oxalic acid, 1 g. sodium chlorite and 0.1 g. of zoylacetaldehydedimethylacetal, dibenzoylmethane, Q- th m d f h f l chloro-malon-(di)aldehyde, acetylacetone or benzoylacetone.

The fluorescent compounds of the Formula I or II are 9 suitable for brightening materials of a great variety, pri- 011350 marily for brightening fibres, filaments, woven and knitted O fabrics, foils or plastic compounds of synthetic origin, e.g. for brightening materials of cellulose esters, polyas brightening agent. The bath is heated to boiling wtihin amides, polyurethanes, polyacrylonitrile and polyesters. 20 minutes and kept at this temperature for 45-60 min- The compounds of the Formula II are particularly suited utes. The polyacrylonitrile fibres are subsequently rinsed for brightening materials of polyacrylonitrile. and dried. The fibres are then outstandingly brightened.

Compounds of the general Formula I suitable to be he brightening agent used was prepared in the folused as brightening agents are set out, by way of example, lowing manner: in the following Table A; the compounds listed in Table A mixture of 254 g. 4-acetylamino-salicylidene-aniline, B as brightening agents of the general Formula II. 153 g., 1,2,4-triazolyl-(l)-'1cetic acid, 99 g. anhydrous s'odium acetate andv510g.- acetic-Eanhydride is heated at aninternaltemperature of 145 C: for 1'2.hours2whi1e stirring. The mixture is then cooledto" 100 .C.'', fol lowedby the addition of 500cc.- concentrated hydrochloric acid in the course of '30 minutes, andthe mixture it. The brightening agents listed" under (a) and (b) are obtained from 7- hydrazino 3-. 5 1,2',4-triazoly1-( 1 couin-arinand malon-(di)aldehydetetraalkyl acetate and subsequent quaternisation of the resultant 7-[Pyrazolyl- 5 (1)] 3 [1,2,4-triazolyl-(1)]-coumarin with dimethyl is boiled under reflux for a further 4 hours. The consulphate'ordiethyl sulphate." The brightening: agent tent Of the flask issubsequentlypoured Oi o 5 li re o is obtained by quaternisation of the above-described 7- ice-water and a pH of,1-.-5 is' adjusted with a concen- [3 methylpyrazolyl (1)] 3 [1,2,4-triazolyl-(1)]- trated sodium hydroxide solution. The -7 ami 0- coumarin with ptoluene-sulphonic acid methyl ester; the y mar n is filtered 1 with Suction, the 10 brightening agent (d byquaternisation ofthe same comiilter cake suspended in 3 litres of water,;and the mixpound ith diethy1.'su1phate,The grbrightening agent (e) ture is rendered ammoniacal. It is again Lfiltered oh with can b synthesised by condensing 7 hydrazino 3 [1,2,4- syq wa he wi t a d gd 3 0;C-. The triazolyl (1)]-coumarin with acetyhacetone and subse- 6 obtained 9? Ii3 01 )179 l? quent quaternisation of 7 [3,5 dimethyl-pyrazolyl(1)]- marin of melting point 265 2;68" Q. f I 15 3... [1,2,4;. triazolyl (1)]-c0umarin with dimethyl 148 g. 7-arnino-3-[1,=2,4-tti "olyl-(l)]-courn ari'ri' are sulphateQBrightening agent (f) is prepared bycondensae dissolved hot in'a mixture of. 750 cc. concentrated hydrotionof 1 b n yl 2 m thb thy l n with 7 [13 chloric acid and 750 ccpof wateia'flhe solution is cooled 'ty 53 1'. i 1 '1f.'. 1) couma in b t0 and dia'zofised With a h h' Sodium quent acidiccyclisation and quaternisation with dimethyl nitrite ill cc} of W jstirrihgis 911m a sulphate-Brightening agentlg) is, obtained by the con.- further hour and the clear diazoniu-m salt,s'olution is then densa tion of 71- hydrazino 3 [1,2,4 triazolyl-(1)]- run into a mixture of 294 (I; and couniarin with aceto-acetaldehyde. in hydrochloric acid 600cc. concentrated hydrochloric a'cideThereac'tion mixd subsequent quaternisation Fin ll th brightening ture is further stirred for one hour and t n poured'into agent (h) is obtained by the condensation of 7-hydrazino- 3 litres of water. The '7-hydrazino-13-[1,2,4-triazolyl-(1)]- 3 2 4 m l (1 -i i 2- 1 coumafhl hydrochloride i p f' Wi hion, suS- malon-(di)aldehyde to give? [4 chloropyrazolyl-(1)]- PFi in 3 litres of m Water n l hh f 3 [1,2,4 triazolyl (l)]-coumarin and subsequent rendered ammoniacal-"lt is again filtered Ofiwith Suction, quaternisation of this compound withdimethyl sulphate. washed with water and dried, There are, obtained 127 g. 7-hydrazino-3-[1,2,4-triazolyl-(1)]-coumarin of melting I N EXAMPLE 2 Pomt (decmPS1.t1n)' One of the brightening agents mentioned in Example 7-hYd1'aZiI10 3 l i i y 1 is added'to a conventional polyacrylonitrile spinning so- 82 g. 3-keto-butyraldehyde-dimethylacetal and 400 cc. lution in such an amount that the concentration of glacial acetic acid are heated to boiling. A dark solution brightening ntin the spun polyacrylonitrile fibre poris formed which is cooled to 60 C. and mixed with 50 tion is 0.1% by Weight. The spinning solution is spun in cc. concentrated hydrochloric acid. The mixture is su'bseusual manner and resultant fibre i l moved q y boiled under reflux a further 2 hours, then about for a further 45 minutes, in a goods-to-liquor ratio mixed with 50 Sodium acetate and filtered OE With 1:40, in an aqueous bath of 95 C. containing, per litre, tion. The filter cake is washed with water and methanol. 1 sodium chlorite and 1 oxalic aid The fib e There are thus obtained 150 g. 7-[3amethyl-pyrazolyltamed then are pure hi (1)] 3 [1,2,4-triazolyl-(1)]-coumarin of melting point 246 C. in the form of small, pale yellow crystals, The EXAMPLE 3 Compound can he Purified y dissolution, -gfrom Fibres of polyethylene glycol terephthalate are intro- DMF glycol'monomethyl ether acetateduced, at a goods-to-liquor ratio 1:40, into a bath which 150 Y -Py Y )l Y contains, per litre, 1 g. oleyl sulphonate, 0.75 g. formic (Ulare dissolved in 10 litresfboiling acid and 0.07 g. of one of the brightening agents set beIlZene- 130 y Sulphate d dmPWiSe to out in the table below. The bath is subsequently heated h Solution f 1S heated 9 a further hourh P to boiling and kept at this temperature for 30-60 minutes. ciprtated quatermsed product is then filtered olf with suc- Aft rinsing and drying the polyestgr fib exhibit 3 tion while hot. The filter cake is washed with methanol. wry good brightening fl t There are obtained 180 g. 7-[3-methyl-pyrazolyl=(11)1 3- [1,2,4-triazolyl-(1)]-coumarin-methosulphate of melting TABLE point 236-238" C. (decomposition) in the form of small, pale yellow crystals. The compound is very readily water- Somme. I

Good brightening effects on polyacrylonitrile fibres are I N o 0 also obtained when, instead of the above-mentioned com- I pound, one of the compounds set out in the following Table are used: Melting /N Brightening agent R1 R2 R3 point, 0. 1 N 1 Y9 H H 273-275 L N l H H 246 GB H H 252 l N 0 H CH 169 o H CH3 189 01 H R1 R: H CuH5 213-214 Brlghten- These brightening agents are produced as described mg R R R Y 93 5 in Example 1, the last step, i.e. the quaternisation, being 2 a s omitted. E i .0 m EXAMPLE 4 H H Chi, nEhdOL- 3 196 A fabric of cellulose triacetate fibres is introduced, at g E 8%: gfigggg: a goods-to-liquor ratio 1:40, into a bath which contains, 3 CH3 8%: :28:: per litre, 1 g. oleyl sulphonate, 0.75 g. formic acid and 0.07 g., of one of the brightening agents mentioned in Example 3. The bath is then heated to 60 C,'within 20 minutes and kept at this. temperature for 30-60 minutes. After rinsing vand drying,- the fabric exhibits a brilliant brightening effect. Y a

.What is-claimedis; a .1. 7 [PY aZlyl-(1')]-3-[l,2,4-triazolyl-(1)]--coumarins oftheformula w where Rq-R5 are as defined above; R is alkyl with 1-4 carbon atoms, or alkyl with 1-4 carbon atoms and a chloro or methoxy substituent;

where R7 and'xRg; are lower;.a1kyl'and-where the phenyl radical cancontain a chloro or ethoxy substituent; and X is-a colorless anion. r u 2. 7 [pyra'z0lyl-( 1) ]-3 [1,2,4-triazoIy1-(l )-coumarins oftthe formula i. a l

. in which R' represents hydr 0'gen, meth'yl or phenyl, and

R to R';, stand for hydrogen, or their quaternisation products of the formula i M v o v v in vwhich R' to R have the same meaning as above, R' stands for methyl orethyl, and X is a colorless anion.

- References Cited UNITED STATES PATENTS 7 3,496,188 2/1970 -Wirth 260310 ALTON DQ ROLLINS, Primary Examiner U.S. c1. X.R. 8-1-W; 106--176; 11743.5 R; 260-141, 308 R UNITED STATES PATENT OFFICER CERTIFICATE OF, CORRECTION Patent No. 3 ,663 ,560 Dated May 16, 1972 Inventor(s) Carl-Wolfgang Schellhammer, Alfons Dorlars and Wolf-Dieter Wirth It is certified that error appears in the above-identified patent and that sid Letters Patent are hereby corrected as shown below:

COLUMN LlZN E ERROR 2 6 "carbonmethoxyphenyl" should be -carbomethoxyphe nyl--.

2 "25 I "R" should be --R 2 I 33 v "an dac etio" jshou-ld beand acetic-m 2 46 1 "7-amino 3- 1,2, 4 should be --7- amino-3 [1,. 2 ,4-

4 68 "wtihin should be -within--.

5 Formula ---R .page 1 F ORM PO-105O (10-69) USCOMM-DC 6O376-P69 u.s. GOVERNMENT PRINTING OFFICE: 1969 0-366-334 UNITED STATES PATENT O'FFICE CERTIFICATE OF CORRECTION Patent No. 3,663,560 Dated May 16 1972 lnventofls) Carl-Wolfgang Schellhammer, Alfons Dorlars and Wolf-Dieter Wirth It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

COLUMN LINE ERROR R W m 5 7 Formula 1 R I l I /N- 3 I 2 7 17 I "benzyl chloro" should be -benzyl, chloro--.

page 2 FORM PC4050 f uscoMM-Dc scan-p69 I Q I U.S. GOVERNMENT PRNTING OFFICE: 1959 0-356-334 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,663,560 Dated May 16 1972 Inventor(s) Carl-Wolfganq Schellhammer Alfons Dorlars and Wolf-Dieter Wirth It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Page 3 COLUMN LINE ERROR- 7 Formula II 5 l q N X I N G) 0 4 I Signed and sealed this 3rd day of December 1974.

(SEAL) Attest:

McCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents USCOMM-DC 60376-P69 & u.s. GOVERNMENT PRINTING omcz: I969 o-ass-au F ORM PO-IO SO (10-69) 

